Triazole derivatives, insecticide, acaricide and methods thereof

ABSTRACT

The invention provides a triazole derivative represented by a general formula ##STR1## (wherein R 1  is an alkyl group, X is a hydrogen atom, a halogen atom or an alkyl group, n is an integer of 1-5, Y is a halogen atom, a nitro group or an alkyl group, and m is an integer of 2-5) as well as insecticide and acaricide containing the same as an active ingredient. 
     The triazole derivatives according to the invention exhibit an excellent effectiveness against harmful pests, particularly aphids and mites.

This application is a division of application Ser. No. 08/338,446 filed 18 Jan. 1994 which application is now U.S. Pat. No. 5,616,914.

TECHNICAL FIELD!

This invention relates to triazole derivatives, insecticides and acaricides containing them as an active ingredient, and methods thereof.

BACKGROUND ART!

As a prior art including compounds similar to the compound according to the invention in the chemical structure, there have hitherto been known the specification of JP-A-56-154464 and technical report RD 278004. They disclose that the compounds have insecticidal and acaricidal activities. However, it can not be said that the compounds described in the above opened specification and technical report are sufficient in the insecticidal and acaricidal activities.

DISCLOSURE OF INVENTION!

The inventors have synthesized various triazole derivatives in order to develop novel and useful insecticide and acraricide and made various studies with respect to physiological activity thereof. As a result, it has been found that the compounds according to the invention have very excellent insecticidal and acaricidal activities against harmful insects and harmful mites as compared with the compounds concretely described in the specification of JP-A-56-154464 and technical report RD 278004. Particularly, it has been found that they are characterized by having plural substituent groups on a benzene ring substituted in 5-position of a triazole ring and have a very excellent insecticidal activity against mites such as two-spotted spider mite, Kanzawa spider mite, citrus red mite and the like; aphids such as cotton aphid and the like; and lepidoptera pests such as diamond-back moth and the like, and as a result the invention has been accomplished.

The invention lies in a triazole derivative represented by a general formula I! ##STR2## {wherein R¹ is an alkyl group, X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group or a trifluoromethyl group, n is an integer of 1-5, provided that when n is 2 or more, X may optionally be same or different combination, Y is a halogen atom, a nitro group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylthioalkyl group, an alkylsulfinylalkyl group, an alkylsulfonylalkyl group, a cycloalkyl group, a cycloalkylalkyl group, a cycloalkylalkenyl group, a cycloalkylalkynyl group, a haloalkyl group, a haloalkoxy group, a trialkylsilylalkyl group, a trialkylsilylalkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group or a group represented by a general formula ##STR3## (wherein A is an oxygen atom, a sulfur atom, a lower alkylene group, a lower alkyleneoxy group, an oxy lower alkylene group, a lower alkyleneoxy lower alkylene group, a lower alkylenethio group, a thio lower alkylene group, a vinylene group or an ethynylene group, k is 0 or 1, Q is a methine group or a nitrogen atom, R² is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-5, provided that when j is 2 or more, R² may optionally be same or different combination), m is an integer of 2-5 and Y may optionally be same or different combination}, and insecticides and acaricides containing the derivative as an active ingredient and methods thereof.

In this specification, the alkyl group means a straight or branched-chain alkyl group having a carbon number of 1-30 and includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isoamyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 4,4-dimethylpentyl group, n-octyl group, 6-methylheptyl group, n-nonyl group, 7-methyloctyl group, n-decyl group, 8-methylnonyl group, n-undecyl group, 9-methyldecyl group, n-dodecyl group, 10-methylundecyl group, n-tridecyl group, 11-methyldodecyl group, n-tetradecyl group, 12-methyltridecyl group, n-pentadecyl group, 13-methyltetradecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

The alkoxy group, alkylthio group, alkylsulfinyl group and alkylsulfonyl group are (alkyl)-O-group, (alkyl)-S-group, (alkyl)-SO-group and (alkyl)-SO₂ -group, in which each alkyl portion has the same meaning as mentioned above. The alkylthioalkyl group, alkylsulfinylalkyl group and alkylsulfonyl group are (alkyl)-S-(alkyl)-group, (alkyl)-SO-(alkyl)-group and (alkyl)-SO₂ -(alkyl)-group, in which each alkyl portion has the same meaning as mentioned above. The halogen atom includes fluorine, chlorine, bromine and iodine.

The alkenyl group means a straight or branched-chain alkenyl group having a carbon number of 2-20 and includes, for example, vinyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, 3-methyl-1-butenyl group, 4-methyl-1-pentenyl group and the like.

The alkynyl group means a straight or branched-chain alkynyl group having a carbon number of 2-20 and includes, for example, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, 3,3-dimethyl-1-butynyl group, 4-methyl-1-pentynyl group, 3-methyl-1-pentynyl group, 5-methyl-1-hexynyl group, 4-methyl-1hexynyl group, 3-methyl-1-hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group and the like.

The cycloalkyl group means a cycloalkyl group having a carbon number of 3-12 and includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. The cycloalkylalkyl group means a cycloalkylalkyl group having a carbon number of 6-12 and includes, for example, cyclopentylmethyl group, cyclohexylmethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclopentylpropyl group, cyclohexylpropyl group, cyclohexylpentyl group and the like.

The cycloalkylalkoxy group means (cycloalkylalkyl)-O-group in which the cycloalkylalkyl portion has the same meaning as mentioned above. The cycloalkylalkenyl group means a cycloalkylalkenyl group having a carbon number of 5-12 and includes, for example, cyclopentylvinyl group, cyclohexylvinyl group, 3-cyclopentyl-1-propenyl group, 3-cyclohexyl-1-propenyl group, 5-cyclohexyl-1-pentenyl group and the like. The cycloalkylalkynyl group means a cycloalkylalkynyl group having a carbon number of 5-12 and includes, for example, cyclopentylethynyl group, cyclohexylethynyl group, 3-cyclopentyl-1-propynyl group, 3-cyclohexyl-1-propynyl group and the like.

The haloalkyl group means an alkyl group substituted with a halogen atom and includes, for example, trifluoromethyl group, pentafluoroethyl group and the like. The haloalkoxy group is (haloalkyl)-O-group in which the haloalkyl portion has the same meaning as described above.

The trialkylsilylalkyl group is, for example, trimethylsilylmethyl group, dimethylethylsilylmethyl group, butyldimethylsilylmethyl group or the like. The trialkylsilylalkoxy group is (trialkylsilylalkyl)-O-group in which the trialkylsilylalkyl portion has the same meaning as described above.

The lower alkylene group includes, for example, methylene group, ethylene group, methylmethylene group, trimethylene group, 1-methylethylene group, dimethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group and the like. The lower alkyleneoxy group is -(lower alkylene)-O-group in which the lower alkylene portion has the same meaning as described above. The oxy lower alkylene group is --O-(lower alkylene)-group in which the lower alkylene portion has the same meaning as described above.

The lower alkyleneoxy lower alkylene group is -(lower alkylene)-O-(lower alkylene)-group in which the lower alkylene portion has the same meaning as described above. The lower alkylenethio group is -(lower alkylene)-S-group in which the lower alkylene portion has the same meaning as described above. The thio lower alkylene group is -S-(lower alkylene)-group in which the lower alkylene portion has the same meaning as described above.

As a preferable compound group in the general formula I!, mention may be made of compounds in which R¹ is a straight or branched-chain alkyl group having a carbon number of 1-6, preferably methyl group, X is a hydrogen atom, a halogen atom, a straight or branched-chain alkyl group having a carbon number of 1-4, a nitro group, a cyano group or a trifluoromethyl group, n is an integer of 1-3 provided that when n is 2 or 3, X may optionally be same or different combination, Y is a halogen atom, a nitro group, a straight or branched-chain alkyl group having a carbon number of 1-20, a straight or branched-chain alkoxy group having a carbon number of 1-20, a cycloalkyl group having a carbon number of 3-12, a cycloalkylalkyl group having a carbon number of 6-12, a cycloalkylalkoxy group having a carbon number of 3-12, a straight or branched-chain alkylthio group having a carbon number of 1-20, an alkylsulfinyl group, an alkylsulfonyl group, a straight or branched-chain alkynyl group having a carbon number of 3-16, a cycloalkylalkynyl group having a carbon number of 5-12, tri(alkyl)silylalkyl group, tri(alkyl)silylalkoxy group or a group represented by the formula: ##STR4## (wherein A is an oxygen atom, a sulfur atom, a lower alkylene group, a lower alkyleneoxy group, an oxy lower alkylene group or a lower alkyleneoxy lower alkylene group, k is 0 or 1, Q is methine group or a nitrogen atom, R² is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-5 provided that when j is 2 or more, R² may optionally be same or different combination), m is an integer of 2-5 and Y may optionally be same or different combination.

The compounds of the general formula I! according to the invention are exemplified in Tables 1-2. Moreover, compound number is referred in subsequent description.

                                      TABLE 1                                      __________________________________________________________________________      ##STR5##                                                                                                   Melting point (°C.)                        Compound                     or refractive                                     No    R.sup.1                                                                            Xn   Ym            index (n.sub.D.sup.20)                            __________________________________________________________________________     1     CH.sub.3                                                                           2-Cl 2-Cl, 3-NO.sub.2                                                                             124.0-125.0                                       2     CH.sub.3                                                                           2 Cl, 6-F                                                                           2-Cl, 3-NO.sub.2                                                                             112.0-114.0                                       3     CH.sub.3                                                                           2-Cl 2-Cl, 4-NO.sub.2                                                4     CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-NO.sub.2                                                                             144.0-148.0                                       5     CH.sub.3                                                                           2-Cl 2-Cl, 5-NO.sub.2                                                                             129.0-130.0                                       6     CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 5-NO.sub.2                                                                             121.0-124.0                                       7     CH.sub.3                                                                           2-Cl 3-NO.sub.2, 4-Cl                                                8     CH.sub.3                                                                           2-Cl, 6-F                                                                           3-NO.sub.2, 4-Cl                                                                             124.0-126.5                                       9     CH.sub.3                                                                           2-Cl 2,6-Cl.sub.2, 3-NO.sub.2                                                                     155.0-156.0                                       10    CH.sub.3                                                                           2-Cl, 6-F                                                                           2,6-Cl.sub.2, 3-NO.sub.2                                                                     108.0-109.0                                       11    CH.sub.3                                                                           2-Cl 2,6-Cl.sub.2, 4-NO.sub.2                                        12    CH.sub.3                                                                           2-Cl, 6-F                                                                           2,6-Cl.sub.2, 4-NO.sub.2                                                                     158.0-162.0                                       13    CH.sub.3                                                                           2-Cl 2,4-Cl.sub.2, 3,5-(NO.sub.2).sub.2                              14    CH.sub.3                                                                           2-Cl, 6-F                                                                           2,4-Cl.sub.2, 3,5-(NO.sub.2).sub.2                              15    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.2 H.sub.5                                                                      75.5-77.5                                         16    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.2 H.sub.5                                                                      1.5930                                            17    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-C.sub.2 H.sub.5                                         18    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.3 H.sub.7                                                                      70.0-72.0                                         19    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.3 H.sub.7                                                                      1.5868                                            20    C.sub.2 H.sub.5                                                                    2-Cl 2-Cl, 4-C.sub.3 H.sub.7                                         21    C.sub.2 H.sub.5                                                                    2-Cl, 6-F                                                                           2-Cl, 4-C.sub.3 H.sub.7                                         22    C.sub.3 H.sub.7 -i                                                                 2-Cl 2-Cl, 4-C.sub.3 H.sub.7                                         23    C.sub.3 H.sub.7 -i                                                                 2-Cl, 6-F                                                                           2-Cl, 4-C.sub.3 H.sub.7                                         24    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.3 H.sub.7 -i                                                                   90.0-92.0                                         25    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.3 H.sub.7 -i                                      26    CH.sub.3                                                                           2-Cl 2,4,6-(C.sub.3 H.sub.7 -i).sub.3                                27    CH.sub.3                                                                           2-Cl, 6-F                                                                           2,4,6-(C.sub.3 H.sub.7 -i).sub.3                                28    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.4 H.sub.9                                                                      1.5962                                            29    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.4 H.sub.9                                                                      1.5667                                            30    CH.sub.3                                                                           H    2-Cl, 5-C.sub.4 H.sub.9 -t                                      31    CH.sub.3                                                                           2-Cl 2-Cl, 5-C.sub.4 H.sub.9 -t                                                                   1.5931                                            32    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 5-C.sub.4 H.sub.9 -t                                                                   1.5943                                            33    CH.sub.3                                                                           2,6-F.sub.2                                                                         2-OC.sub.2 H.sub.5, 4-C.sub.4 H.sub.9 -t                                                     146.0-148.0                                       34    CH.sub.3                                                                           2-Cl 2-OC.sub.2 H.sub.5, 4-C.sub.4 H.sub.9 -t                                                     1.5818                                            35    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-OC.sub.2 H.sub.5, 4-C.sub.4 H.sub.9 -t                                                     108.0-111.0                                       36    CH.sub.3                                                                           2,6-F.sub.2                                                                         2-Cl, 4-C.sub.5 H.sub.11                                                                     1.5629                                            37    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.5 H.sub.11                                                                     1.5849                                            38    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.5 H.sub.11                                                                     1.5710                                            39    CH.sub.3                                                                           2,6-F.sub.2                                                                         2-Cl, 4-C.sub.6 H.sub.13                                                                     1.5591                                            40    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.6 H.sub.13                                                                     1.5830                                            41    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.6 H.sub.13                                                                     1.5638                                            42    CH.sub.3                                                                           2-Cl 2-F, 5-C.sub.6 H.sub.13                                                                      1.5779                                            43    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-F, 5-C.sub.6 H.sub.13                                                                      1.5608                                            44    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.7 H.sub.15                                                                     1.5824                                            45    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.7 H.sub.15                                        46    CH.sub.3                                                                           2,6-F.sub.2                                                                         2-F, 5-C.sub.11 H.sub.23                                                                     70.0-73.0                                         47    CH.sub.3                                                                           2-Cl 2-F, 5-C.sub.11 H.sub.23                                                                     35.0-37.0                                         48    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-F, 5-C.sub.11 H.sub.23                                                                     1.5419                                            49    CH.sub.3                                                                           2,6-F.sub.2                                                                         2-Cl, 4-C.sub.12 H.sub.25                                       50    CH.sub.3                                                                           2-Cl 2-Cl, 4-C.sub.12 H.sub.25                                                                    76.0-77.0                                         51    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-C.sub.12 H.sub.25                                                                    1.5490                                            52    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-C.sub.15 H.sub.31                                       53    CH.sub.3                                                                           H    3,5-(OC.sub.2 H.sub.5).sub.2                                    54    CH.sub.3                                                                           2-CH.sub.3                                                                          3,5-(OC.sub.2 H.sub.5).sub.2                                    55    CH.sub.3                                                                           2-OCH.sub.3                                                                         3,5-(OC.sub.2 H.sub.5).sub.2                                    56    CH.sub.3                                                                           2-SCH.sub.3                                                                         3,5-(OC.sub.2 H.sub.5).sub.2                                    57    CH.sub.3                                                                           2-NO.sub.2                                                                          3,5-(OC.sub.2 H.sub.5).sub.2                                    58    CH.sub.3                                                                           2-CN 3,5-(OC.sub.2 H.sub.5).sub.2                                    59    CH.sub.3                                                                           2-CF.sub.3                                                                          3,5-(OC.sub.2 H.sub.5).sub.2                                    60    CH.sub.3                                                                           2-Cl 2-OC.sub.2 H.sub.5, 4,5-Cl.sub.2                                61    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-OC.sub.2 H.sub.5, 4,5-Cl.sub.2                                                             115.0-117.0                                       62    CH.sub.3                                                                           2-Cl 2-OC.sub.2 H.sub.5, 4,5-F.sub.2                                 63    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-OC.sub.2 H.sub.5, 4,5-F.sub.2                                                              1.5590                                            64    CH.sub.3                                                                           2-Cl 2-Cl, 4-OC.sub.4 H.sub.9                                                                     60.0-62.0                                         65    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-OC.sub.4 H.sub.9                                                                     1.5631                                            66    CH.sub.3                                                                           2-Cl 2-Cl, 4-OC.sub.5 H.sub.11                                                                    71.0-73.0                                         67    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-OC.sub.5 H.sub.11                                       68    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-OC.sub.5 H.sub.11, 4-Cl                                                                    not measurable                                    69    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-OC.sub.5 H.sub.11, 4-Cl                                       70    CH.sub.3                                                                           2-Cl 3,5-(OC.sub.5 H.sub.11).sub.2                                   71    CH.sub.3                                                                           2-Cl, 6-F                                                                           3,5-(OC.sub.5 H.sub.11).sub.2                                   72    CH.sub.3                                                                           2,6-Cl.sub.2                                                                        2-Cl, 4-OC.sub.8 H.sub.17                                                                    1.5728                                            73    CH.sub.3                                                                           2-Cl 2-Cl, 4-OC.sub.8 H.sub.17                                                                    51.0-54.0                                         74    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-OC.sub.8 H.sub.17                                                                    1.5641                                            75    CH.sub.3                                                                           2-Cl 3-Cl, 4-OC.sub.8 H.sub.17                                                                    47.0-49.0                                         76    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-OC.sub.8 H.sub.17                                                                    1.5658                                            77    CH.sub.3                                                                           2-Cl 3-OC.sub.8 H.sub.17, 4-Cl                                                                    not measurable                                    78    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-OC.sub.8 H.sub.17, 4-Cl                                                                    1.5658                                            79    CH.sub.3                                                                           2-Cl 3,5-(OC.sub.8 H.sub.17).sub.2                                   80    CH.sub.3                                                                           2-Cl, 6-F                                                                           3,5-(OC.sub.8 H.sub.17).sub.2                                   81    CH.sub.3                                                                           2-NO.sub.2                                                                          3-Cl, 4-OC.sub.12 H.sub.25                                      82    CH.sub.3                                                                           2-SCH.sub.3                                                                         3-Cl, 4-OC.sub.12 H.sub.25                                      83    CH.sub.3                                                                           2-Cl 3-Cl, 4-OC.sub.15 H.sub.31                                      84    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-OC.sub.15 H.sub.31                                      85    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-CH.sub.2 OCH.sub.3                                      86    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-(CH.sub.2).sub.3 OC.sub.3 H.sub.7                       87    CH.sub.3                                                                           2-Cl 2-Cl, 4-OC.sub.2 H.sub.4 OCH.sub.3                                                           1.5946                                            88    CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-OC.sub.2 H.sub.4 OCH.sub.3                              89    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SCH.sub.3, 4-Cl                                               90    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SC.sub.3 H.sub.7, 4-Cl                                        91    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SC.sub.6 H.sub.13, 4-Cl                                       92    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SOCH.sub.3, 4-Cl                                              93    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SOC.sub.3 H.sub.7, 4-Cl                                       94    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SOC.sub.6 H.sub.13, 4-Cl                                      95    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SO.sub.2 CH.sub.3, 4-Cl                                       96    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SO.sub.2 C.sub.3 H.sub.7, 4-Cl                                97    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-SO.sub.2 C.sub.6 H.sub.13, 4-Cl                               98    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SCH.sub.3, 4-C.sub.2 H.sub.5                         99    CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SC.sub.3 H.sub.7, 4-C.sub.2 H.sub.5                  100   CH.sub.3                                                                           2-Cl 3-Br, 4-CH.sub.2 SC.sub.5 H.sub.11                              101   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Br, 4-CH.sub.2 SC.sub.5 H.sub.11                              102   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SC.sub.6 H.sub.13, 4-C.sub.2 H.sub.5                 103   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SOCH.sub.3, 4-C.sub.2 H.sub.5                        104   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SOC.sub.3 H.sub.7, 4-C.sub.2 H.sub.5                 105   CH.sub.3                                                                           2-Cl 3-Br, 4-CH.sub.2 SOC.sub.5 H.sub.11                             106   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Br, 4-CH.sub.2 SOC.sub.5 H.sub.11                             107   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SOC.sub.6 H.sub.13, 4-C.sub.2 H.sub.5                108   CH.sub.3                                                                           2-Cl 3-Br, 4-CH.sub.2 SO.sub.2 C.sub.5 H.sub.11                      109   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Br, 4-CH.sub.2 SO.sub.2 C.sub.5 H.sub.11                      110   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SO.sub.2 CH.sub.3, 4-C.sub.2 H.sub.5                 111   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SO.sub.2 C.sub.3 H.sub.7, 4-C.sub.2 H.sub.5          112   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 SO.sub.2 C.sub.6 H.sub.13, 4-C.sub.2 H.sub.5         113   CH.sub.3                                                                           2-Cl 2-Cl, 5-C.sub.2 F.sub.5                                         114   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 5-C.sub.2 F.sub.5                                         115   CH.sub.3                                                                           2-Cl 2-Cl, 5-C.sub.4 F.sub.9                                         116   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 5-C.sub.4 F.sub.9                                                                      1.5110                                            117   CH.sub.3                                                                           2-Cl 3-C.sub.4 F.sub.9, 4-Cl                                         118   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-C.sub.4 F.sub.9, 4-Cl                                                                      1.5392                                            119   CH.sub.3                                                                           2-Cl 2-Cl, 5-C.sub.6 F.sub.13                                                                     70.0-76.0                                         120   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 5-C.sub.6 F.sub.13                                                                     78.0-82.0                                         121   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-F, 5-C.sub.4 H.sub.9                                                                       1.5090                                            122   CH.sub.3                                                                           2-Cl 3, 5-Cl.sub.2, 5-C.sub.8 H.sub.17                               123   CH.sub.3                                                                           2-Cl, 6-F                                                                           3, 5-Cl.sub.2, 5-O(CF.sub.2).sub.2 H                                                          96.0-101.0                                       124   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-(CH.sub.2).sub.2 C.sub.4 F.sub.9                        125   CH.sub.3                                                                           2-Cl 2-Cl, 5-OC.sub.2 F.sub.5                                        126   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 5-OC.sub.2 F.sub.5                                        127   CH.sub.3                                                                           2-Cl 3-Cl, 4-O(CH.sub.2).sub.2 C.sub.4 F.sub.9                       128   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-O(CH.sub.2).sub.2 C.sub.4 F.sub.9                       129   CH.sub.3                                                                           2-Cl 3-Br, 4-CH.sub.2 Si(CH.sub.3).sub.3                             130   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Br, 4-CH.sub.2 Si(CH.sub.3).sub.3                             131   CH.sub.3                                                                           2-Cl 3-Br, 4-OCH.sub.2 Si(CH.sub.3).sub.3                            132   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Br, 4-OCH.sub.2 Si(CH.sub.3).sub.3                            133   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CHCH.sub.2, 4-Cl                                              134   CH.sub.3                                                                           2-Cl 3-Br, 4-CHCHCH.sub.3                                            135   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Br, 4-CHCHCH.sub.3                                            136   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-CH.sub.2 CHCHC.sub.3 H.sub.7, 4-Cl                            137   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-OCHCH.sub.2, 4-Cl                                             138   CH.sub.3                                                                           2-Cl 2-Cl, 4-OCHCH.sub.2                                                                          1.6083                                            139   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-OCHCH.sub.2                                             140   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-OCH.sub.2 CHCHC.sub.3 H.sub.7, 4-Cl                           141   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-C CH                                                    142   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-C CC.sub.4 H.sub.9                                      143   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-OC CH                                                   144   CH.sub.3                                                                           2-Cl, 6-F                                                                           3-Cl, 4-OC CC.sub.4 H.sub.9                                     145   CH.sub.3                                                                           2-Cl 2-Cl, 4-OCH.sub.2 C CH                                                                       103.5-105.0                                       146   CH.sub.3                                                                           2-Cl, 6-F                                                                           2-Cl, 4-OCH.sub.2 C CH                                          147   CH.sub.3                                                                           2-Cl                                                                                 ##STR6##                                                       148   CH.sub.3                                                                           2-Cl, 6-F                                                                            ##STR7##                                                       149   CH.sub.3                                                                           2-Cl                                                                                 ##STR8##                                                       150   CH.sub.3                                                                           2-Cl, 6-F                                                                            ##STR9##                                                       151   CH.sub.3                                                                           2-Cl                                                                                 ##STR10##                                                      152   CH.sub.3                                                                           2-Cl, 6-F                                                                            ##STR11##                                                      153   CH.sub.3                                                                           2-Cl                                                                                 ##STR12##                                                      154   CH.sub.3                                                                           2-Cl, 6-F                                                                            ##STR13##                                                      __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR14##                                                                                                          Melting point (°C.)                Compound                             or refractive                             No.   R.sup.1                                                                           Xn    R.sup.4               index (n.sub.D.sup.20)                    __________________________________________________________________________     155   CH.sub.3                                                                          2-Cl                                                                                  ##STR15##                                                      156   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR16##                                                      157   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR17##            117.0-119.0                               158   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR18##            1.5925                                    159   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR19##                                                      160   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR20##                                                      161   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR21##            179.0-185.0                               162   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR22##                                                      163   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR23##                                                      164   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR24##                                                      165   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR25##                                                      166   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR26##                                                      167   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR27##                                                      168   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR28##                                                      169   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR29##                                                      170   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR30##                                                      171   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR31##                                                      172   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR32##                                                      173   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR33##                                                      174   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR34##                                                      175   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR35##                                                      176   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR36##                                                      177   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR37##                                                      178   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR38##                                                      179   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR39##                                                      180   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR40##                                                      181   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR41##                                                      182   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR42##                                                      183   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR43##                                                      184   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR44##                                                      185   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR45##                                                      186   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR46##                                                      187   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR47##                                                      188   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR48##                                                      189   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR49##                                                      190   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR50##                                                      191   CH.sub.3                                                                          2-Cl                                                                                  ##STR51##                                                      192   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR52##                                                      193   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR53##                                                      194   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR54##                                                      195   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR55##                                                      196   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR56##            113.0-114.0                               197   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR57##            1.6010                                    198   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR58##                                                      199   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR59##            1.5961                                    200   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR60##                                                      201   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR61##            1.5701                                    202   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR62##                                                      203   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR63##                                                      204   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR64##                                                      205   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR65##                                                      206   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR66##                                                      207   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR67##                                                      208   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR68##                                                      209   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR69##                                                      210   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR70##                                                      211   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR71##                                                      212   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR72##                                                      213   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR73##                                                      214   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR74##                                                      215   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR75##                                                      216   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR76##                                                      217   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR77##                                                      218   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR78##                                                      219   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR79##                                                      220   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR80##                                                      221   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR81##                                                      222   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR82##                                                      223   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR83##                                                      224   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR84##                                                      225   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR85##                                                      226   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR86##                                                      227   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR87##                                                      228   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR88##                                                      229   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR89##                                                      230   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR90##                                                      231   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR91##                                                      232   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR92##                                                      233   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR93##                                                      234   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR94##                                                      235   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR95##                                                      236   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR96##                                                      237   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR97##                                                      238   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR98##                                                      239   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR99##                                                      240   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR100##                                                     241   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR101##           135.0-140.0                               242   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR102##                                                     243   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR103##                                                     244   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR104##                                                     245   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR105##                                                     246   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR106##                                                     247   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR107##                                                     248   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR108##                                                     249   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR109##                                                     250   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR110##                                                     251   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR111##                                                     252   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR112##                                                     253   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR113##                                                     254   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR114##                                                     255   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR115##                                                     256   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR116##                                                     257   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR117##                                                     258   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR118##                                                     259   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR119##           67.0-72.0                                 260   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR120##                                                     261   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR121##                                                     262   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR122##                                                     263   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR123##                                                     264   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR124##                                                     265   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR125##                                                     266   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR126##                                                     267   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR127##           101.0-107.0                               268   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR128##           115.0-120.0                               269   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR129##           74.0-77.0                                 270   CH.sub.3                                                                          2-Cl                                                                                  ##STR130##                                                     271   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR131##                                                     272   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR132##                                                     273   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR133##           156.0-159.0                               274   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR134##           109.0-111.0                               275   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR135##           43.0-47.0                                 276   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR136##           171.0-177.0                               277   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR137##           1.5680                                    278   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR138##           132.0-136.0                               279   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR139##                                                     280   CH.sub.3                                                                          2-Cl                                                                                  ##STR140##                                                     281   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR141##                                                     282   CH.sub.3                                                                          2-Cl                                                                                  ##STR142##                                                     283   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR143##                                                     284   CH.sub.3                                                                          2-Cl                                                                                  ##STR144##                                                     285   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR145##                                                     286   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR146##                                                     287   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR147##                                                     288   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR148##                                                     289   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR149##                                                     290   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR150##                                                     291   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR151##                                                     292   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR152##                                                     293   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR153##                                                     294   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR154##                                                     295   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR155##                                                     296   CH.sub.3                                                                          2-Cl                                                                                  ##STR156##                                                     297   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR157##                                                     298   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR158##                                                     299   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR159##                                                     300   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR160##                                                     301   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR161##                                                     302   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR162##                                                     303   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR163##                                                     304   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR164##                                                     305   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR165##                                                     306   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR166##                                                     307   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR167##                                                     308   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR168##                                                     309   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR169##                                                     310   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR170##                                                     311   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR171##           135.0-139.0                               312   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR172##                                                     313   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR173##           109.0-112.0                               314   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR174##                                                     315   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR175##                                                     316   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR176##                                                     317   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR177##           not measurable                            318   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR178##                                                     319   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR179##           1.5698                                    320   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR180##           123.5-126.0                               321   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR181##           1.5638                                    322   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR182##           137.0-141.0                               323   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR183##                                                     324   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR184##                                                     325   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR185##                                                     326   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR186##                                                     327   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR187##                                                     328   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR188##                                                     329   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR189##                                                     330   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR190##           153.0-155.0                               331   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR191##                                                     332   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR192##           47.0-49.0                                 333   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR193##                                                     334   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR194##           1.5879                                    335   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR195##                                                     336   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR196##                                                     337   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR197##                                                     338   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR198##           88.0-90.0                                 339   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR199##                                                     340   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR200##                                                     341   CH.sub.3                                                                          2-Cl                                                                                  ##STR201##                                                     342   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR202##                                                     343   CH.sub.3                                                                          2-Cl                                                                                  ##STR203##                                                     344   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR204##                                                     345   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR205##           109.5-112.0                               346   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR206##                                                     347   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR207##                                                     348   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR208##                                                     349   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR209##                                                     350   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR210##                                                     351   CH.sub.3                                                                          2-Cl                                                                                  ##STR211##                                                     352   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR212##                                                     353   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR213##                                                     354   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR214##                                                     355   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR215##                                                     356   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR216##                                                     357   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR217##                                                     358   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR218##                                                     359   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR219##                                                     360   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR220##                                                     361   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR221##                                                     362   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR222##                                                     363   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR223##                                                     364   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR224##                                                     365   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR225##                                                     366   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR226##                                                     367   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR227##                                                     368   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR228##                                                     369   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR229##                                                     370   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR230##                                                     371   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR231##                                                     372   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR232##                                                     373   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR233##           1.5391                                    374   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR234##           108.0-111.0                               375   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR235##                                                     376   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR236##           58.0-62.0                                 377   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR237##           not measurable                            378   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR238##           not measurable                            379   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR239##                                                     380   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR240##                                                     381   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR241##                                                     382   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR242##                                                     383   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR243##                                                     384   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR244##                                                     385   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR245##                                                     386   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR246##                                                     387   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR247##                                                     388   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR248##                                                     389   CH.sub.3                                                                          2-Cl                                                                                  ##STR249##           104.0-108.0                               390   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR250##           139.0-141.0                               391   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR251##           110.0-112.0                               392   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR252##                                                     393   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR253##                                                     394   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR254##                                                     395   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR255##           127.0-132.0                               396   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR256##                                                     397   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR257##                                                     398   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR258##                                                     399   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR259##                                                     400   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR260##           129.0-130.0                               401   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR261##           not measurable                            402   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR262##                                                     403   CH.sub.3                                                                          2-Cl                                                                                  ##STR263##           150.0-152.0                               404   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR264##           149.0-151.5                               405   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR265##                                                     406   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR266##           140.0-144.0                               407   CH.sub.2                                                                          2,6-F.sub.2                                                                           ##STR267##                                                     408   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR268##                                                     409   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR269##           not measurable                            410   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR270##           not measurable                            411   CH.sub.3                                                                          2,3,4,5,6-F.sub.5                                                                     ##STR271##                                                     412   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR272##           not measurable                            413   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR273##           116.0-117.0                               414   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR274##                                                     415   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR275##                                                     416   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR276##                                                     417   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR277##                                                     418   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR278##                                                     419   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR279##           120.0-123.0                               420   CH.sub.3                                                                          2-Cl                                                                                  ##STR280##                                                     421   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR281##                                                     422   CH.sub.3                                                                          2-Cl                                                                                  ##STR282##                                                     423   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR283##                                                     424   CH.sub.3                                                                          2-Cl                                                                                  ##STR284##                                                     425   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR285##                                                     426   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR286##                                                     427   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR287##                                                     428   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR288##                                                     429   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR289##                                                     430   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR290##                                                     431   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR291##                                                     432   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR292##                                                     433   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR293##                                                     434   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR294##                                                     435   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR295##                                                     436   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR296##                                                     437   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR297##                                                     438   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR298##                                                     439   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR299##                                                     440   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR300##                                                     441   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR301##                                                     442   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR302##                                                     443   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR303##                                                     444   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR304##                                                     445   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR305##                                                     446   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR306##                                                     447   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR307##                                                     448   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR308##                                                     449   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR309##                                                     450   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR310##                                                     451   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR311##           123.0-127.0                               452   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR312##                                                     453   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR313##           1.5020                                    454   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR314##                                                     455   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR315##                                                     456   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR316##           78.0-83.0                                 457   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR317##           117.0-122.0                               458   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR318##                                                     459   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR319##                                                     460   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR320##                                                     461   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR321##                                                     462   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR322##                                                     463   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR323##                                                     464   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR324##                                                     465   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR325##                                                     466   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR326##                                                     467   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR327##                                                     468   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR328##                                                     469   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR329##                                                     470   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR330##                                                     471   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR331##                                                     472   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR332##                                                     473   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR333##                                                     474   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR334##                                                     475   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR335##                                                     476   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR336##                                                     477   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR337##                                                     478   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR338##                                                     479   CH.sub.3                                                                          2-Cl                                                                                  ##STR339##                                                     480   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR340##           116.0-119.0                               481   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR341##                                                     482   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR342##                                                     483   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR343##                                                     484   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR344##                                                     485   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR345##                                                     486   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR346##                                                     487   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR347##                                                     488   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR348##                                                     489   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR349##           129.0-131.0                               490   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR350##                                                     491   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR351##                                                     492   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR352##                                                     493   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR353##                                                     494   CH.sub.3                                                                          2-Cl                                                                                  ##STR354##                                                     495   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR355##                                                     496   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR356##            97.0-102.0                               497   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR357##           74.0-79.0                                 498   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR358##           129.0-134.0                               499   CH.sub.3                                                                          2-Cl                                                                                  ##STR359##                                                     500   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR360##                                                     501   CH.sub.3                                                                          2-Cl                                                                                  ##STR361##                                                     502   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR362##                                                     503   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR363##                                                     504   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR364##                                                     505   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR365##                                                     506   CH.sub.3                                                                          2-Cl                                                                                  ##STR366##                                                     507   CH.sub.3                                                                          2-Cl                                                                                  ##STR367##                                                     508   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR368##           142.0-144.0                               509   CH.sub.3                                                                          2-Cl                                                                                  ##STR369##           not measurable                            510   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR370##           not measurable                            511   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR371##           1.6087                                    512   CH.sub.3                                                                          2-Cl                                                                                  ##STR372##                                                     513   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR373##           105.0-109.0                               514   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR374##           155.0-157.0                               515   CH.sub.3                                                                          2-Cl                                                                                  ##STR375##                                                     516   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR376##           not measurable                            517   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR377##           not measurable                            518   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR378##                                                     519   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR379##                                                     520   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR380##                                                     521   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR381##                                                     522   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR382##           140.0-143.0                               523   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR383##           not measurable                            524   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR384##           not measurable                            525   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR385##                                                     526   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR386##           not measurable                            527   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR387##                                                     528   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR388##                                                     529   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR389##                                                     530   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR390##                                                     531   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR391##           102.0-104.0                               532   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR392##                                                     533   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR393##                                                     534   CH.sub.3                                                                          2,6-F.sub.2                                                                           ##STR394##                                                     535   CH.sub.3                                                                          2-Cl, 6-F                                                                             ##STR395##                                                     __________________________________________________________________________

The compounds according to the invention can be produced according to the following methods.

Production Method 1-1 ##STR396## (wherein W is a sulfur atom or an oxygen atom, L is an alkyl group having a carbon number of 1-4, and R¹, X, n, Y and m are the same as mentioned above).

That is, the compound according to the invention represented by the general formula I! can be obtained by reacting an N-acylimidate derivative or N-acylthioimidate derivative represented by a general formula II! with a hydrazine derivative represented by a general formula III! in an inert solvent.

As the solvent, any solvents not obstructing the reaction can be used, which include, for example, alcohols such as methanol, ethanol and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; water and a mixed solvent comprised of a combination of solvents selected from the above. Furthermore, the amount of the starting material used is usually 1.0-5.0 moles of the compound shown by the general formula III! per 1 mole of the compound shown by the general formula II!.

The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-72 hours. A concrete example of this reaction is described, for example, in Synthesis, page 483 (1983).

The starting compound shown by the general formula II! can be produced by the following method.

Production Method 1-2 ##STR397## (wherein Z is a halogen atom, and L, W, X, n, Y and m are the same as mentioned above).

That is, the compound shown by the general formula II! can be obtained by reacting a compound of a general formula IV! with a compound of a general formula V! in the presence of a base in an inert solvent. The compound of the general formula IV! may be an acid addition salt such as a salt with boron tetrafluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide or the like.

As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; and organic bases such as diethylamine, triethylamine, pyridine, 4-(N,N-dimethylamino) pyridine and the like.

As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the reactant used is usually 0.8-1.3 moles of the compound shown by the general formula V! per 1 mole of the compound shown by the general formula IV!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula IV!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-24 hours.

Production Method 2 ##STR398## (wherein R¹, X, n, Y and m are the same as mentioned above, and R³ is a phenyl group, which may be substituted with an alkyl group having a carbon number of 1-4, or an alkyl group having a carbon number of 1-4).

That is, the compound of the general formula I! according to the invention can be obtained by reacting a benzohydrazonoyl chloride derivative represented by a general formula VI! with a benzonitrile derivative represented by a general formula VII! in the presence of a Lewis acid in an inert solvent.

As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme, 1,2-dimethoxyethane and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as nitrobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; a mixed solvent comprised of a combination of solvents selected from the above.

As the Lewis acid, use may be made of aluminum bromide, aluminum chloride, iron (III) chloride, boron trifluoride, titanium tetrachloride and so on. Furthermore, the amounts of the starting material and the like used are usually 1.0-2.0 moles of the compound shown by the general formula VII! and 1.0-2.0 moles of the Lewis acid per 1 mole of the compound shown by the general formula VI!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object Tan usually be attained for 30 minutes-5 hours. A concrete example of this reaction is described, for example, in Bulltein of the Chemical Society of Japan (Bull. Chem. Soc. Jpn), vol. 56, page 545 (1983).

Production Method 3-1 ##STR399## (wherein R¹, R³, X, n, Y, m and Z are the same as mentioned above).

That is, the compound of the general formula I! according to the invention can be obtained by reacting a benzamidrazone derivative of a general formula VIII! with a benzoylhalide derivative of a general formula V! in the absence of a solvent or in an inert solvent.

As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrolidinone and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the starting material used is usually 1.0-2.0 moles of the compound shown by the general formula V! per 1 mole of the compound shown by the general formula VIII!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-5 hours. A concrete example of this reaction is described, for example, in Bulltein of the Chemical Society of Japan (Bull. Chem. Soc. Jpn), vol. 56, page 545 (1983).

Moreover, the compound of the general formula VIII! as a starting material can be produced by the following method.

Production Method 3-2 ##STR400## (wherein R¹, R³, X and n are the same as mentioned above).

The compound of the general formula VIII! can be obtained by reacting a compound of a general formula VI! with an ammonia gas in an inert solvent.

As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the starting material used is usually 5.0-10.0 moles of ammonia per 1 mole of the compound shown by the general formula VI!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-24 hours. A concrete example of this reaction is described, for example, in Bulltein of the Chemical Society of Japan (Bull. Chem. Soc. Jpn), vol. 56, page 545 (1983).

Production Method 4-1 ##STR401## (wherein X, R¹, Y', n and m' are the same as mentioned above).

A compound of a general formula X! can be obtained by reacting a compound of a general formula IX! in the presence of a Lewis acid in an inert solvent.

As the Lewis acid, use may be made of aluminum bromide, aluminum chloride, iron (III) chloride, boron trifluoride, titanium tetrachloride and so on.

As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as nitrobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the reactant used is usually 1.0-5.0 moles of the Lewis acid per 1 mole of the compound shown by the general formula IX!. The reaction temperature is within a range of from -20° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-24 hours.

Production Method 4-2 ##STR402## wherein B is a halogen atom, R⁴ --SO₂ -group or R⁴ --SO₃ -group (R⁴ is an alkyl group having a carbon number of 1-4 or a phenyl group which may be substituted), k is 0 or 1, and X, Y', R¹, R², Q, j, m' and n are the same as mentioned above).

The compound of a general formula XII! according to the invention can be obtained by reacting a compound of a general formula X! with a compound of a general formula XI! in the presence of a base in an inert solvent.

As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; metal hydrides such as sodium hydride, poptassium hydride and the like; and organic bases such as triethylamine, pyridine and the like.

As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and the like; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and the like; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the reactant used is usually 1.0-2.0 moles of the compound shown by the general formula XI! per 1 mole of the compound shown by the general formula X!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula X!. The reaction temperature is within a range of from -20° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.

Production Method 5-1 ##STR403## (wherein X, R¹, Z, Y', n and m' are the same as mentioned above).

A compound of a general formula XIV! can be obtained from a triazole derivative of a general formula XIII! with a halogenating agent. This compound can be reacted with an acetoxylating agent to obtain a compound of a general formula XV!. Then, the compound of the general formula XV! can be reacted with an acid or alkali to obtain a compound of a general formula XVI!.

As the halogenating agent used in the step A, use may be made of, for example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide and so on.

As the solvent used, mention may be made of aromatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on. Furthermore, it is required to use a catalytic amount of benzoyl peroxide, azobisisobutyronitrile or the like as a radical initiator in this reaction.

The amount of the halogenating agent used is usually 0.8-1.5 moles per 1 mole of the compound shown by the general formula XIII!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-12 hours.

As the acetoxylating agent used in the step B, use may be made of lithium acetate, sodium acetate, potassium acetate, calcium acetate and so on.

As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the acetoxylating agent used is usually 1.0-4.0 moles per 1 mole of the compound shown by the general formula XIV!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.

As the acid used in the step C, use may be made of mineral acids such as hydrochloric acid, sulfuric acid and so on; and Lewis acids such as aluminum bromide, aluminum chloride and so on. In this case, as the solvent, use may be made of carboxylic acids such as acetic acid, formic acid and so on; ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and so on; aromatic hydrocarbons such as benzene, toluene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and so on; water and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the acid used is usually a catalytic amount--4.0 moles per 1 mole of the compound shown by the general formula XV!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-24 hours.

As the alkali used in the step C, use may be made of aqueous solutions of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and so on. In this case, as the solvent, use may be made of alcohols such as methanol, ethanol, ethylene glycol and so on; ketones such as acetone, methyl ethyl ketone and so on; ethers such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane and so on; water and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the alkali used is usually 0.5-4.0 moles per 1 mole of the compound shown by the general formula XV!. The reaction temperature is within a range of from 0° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-24 hours.

Production Method 5-2 ##STR404## (wherein X, Y', B, Q, R¹, R², j, k, m' and n are the same as mentioned above).

The compound shown by the general formula XVII! according to the invention can be obtained by reacting a compound of a general formula XVI! with a compound of a general formula XI! in the presence of a base in an inert solvent.

As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; metal hydrides such as sodium hydride, potassium hydride and the like; and organic bases such as triethylamine, pyridine and the like.

As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the reactant used is usually 1.0-2.0 moles of the compound shown by the general formula XI! per 1 mole of the compound shown by the general formula XVI!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula XVI!. The reaction temperature is within a range of from -20° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.

Production Method 5-3 ##STR405## (wherein X, Y', Q, R¹, R², Z, j, k, m' and n are the same as mentioned above).

The compound shown by the general formula XVII! according to the invention can be obtained by reacting a compound of the general formula XIV! with a compound of the general formula XVIII! in the presence of a base in an inert solvent.

As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; metal hydrides such as sodium hydride, potassium hydride and the like; and organic bases such as triethylamine, pyridine and the like.

As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.

The amount of the reactant used is usually 1.0-2.0 moles of the compound shown by the general formula XVIII! per 1 mole of the compound shown by the general formula XIV!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula XIV!. The reaction temperature is within a range of from -20° C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.

BEST MODE FOR CARRYING OUT THE INVENTION!

The preparation method of the compounds according to the invention, formulation method and applications will concretely be described with reference to the following examples.

EXAMPLE 1 Preparation of 3-(2-chlorophenyl)-5-(2-chloro-3-nitrophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 1)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (1.72 g), 2-chloro-3-nitrobenzonitrile (1.00 g), anhydrous aluminum chloride (0.70 g) and o-dichlorobenzene (20 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.12 g of desired compound (melting point: 124.0°-125.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.83           (3H, s)                                                         7.16-8.10      (7H, m)                                                  ______________________________________                                    

EXAMPLE 2 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-3-nitrophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 2)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.90 g), 2-chloro-3-nitrobenzonitrile (1.19 g), anhydrous aluminum chloride (0.70 g) and o-dichlorobenzene (20 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.19 g of desired compound (melting point: 112.0°-114.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.90           (3H, s)                                                         6.90-8.10      (6H, m)                                                  ______________________________________                                    

EXAMPLE 3 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-nitrophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 4)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.90 g), 2-chloro-4-nitrobenzonitrile (1.80 g), anhydrous iron (III) chloride (1.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 2.20 g of desired compound (melting point: 144.0°-148.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.88           (3H, s)                                                         6.90-8.46      (6H, m)                                                  ______________________________________                                    

EXAMPLE 4 Preparation of 5-(2-chloro-4-ethylphenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 15)

Ethyl 2-chlorobenzimidate (2.75 g) and triethylamine (1.60 g) are dissolved in toluene (30 ml) and 2-chloro-4-ethylbenzoyl chloride (2.64 g) is added dropwise thereto within a range of 5° C.-15° C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 3 hours. After cooling to room temperature, the reaction mixture is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (1.00 g) and stirred at room temperature for 16 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.10 g of desired compound (melting point: 75.5°-77.5° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                1.27           (3H, t)                                                         2.70           (2H, q)                                                         3.83           (3H, s)                                                         7.10-7.60      (6H, m)                                                         7.90-8.10      (1H, m)                                                  ______________________________________                                    

EXAMPLE 5 Preparation of 5-(2-chloro-4-ethylphenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 16)

Ethyl 2-chloro-6-fluorobenzimidate (3.02 g) and triethylamine (1.60 g) are dissolved in toluene (30 ml) and 2-chloro-4-ethylbenzoyl chloride (2.64 g) is added dropwise thereto within a range of 5° C.-15° C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and heated under reflux for 2 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.63 g of desired compound (refractive index: 1.5930).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                1.26           (3H, t)                                                         2.69           (2H, q)                                                         3.83           (3H, s)                                                         6.90-7.50      (6H, m)                                                  ______________________________________                                    

EXAMPLE 6 Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-propylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 18)

Ethyl 2-chlorobenzimidate (2.75 g) and triethylamine (1.80 g) are dissolved in toluene (30 ml) and 2-chloro-4-propylbenzoyl chloride (3.30 g) is added dropwise thereto within a range of 5° C.-15° C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 1 hour. After cooling to room temperature, the reaction solution is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.80 g) and stirred at room temperature for 18 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.78 g of desired compound (melting point: 70.0°-72.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.95           (3H, t)                                                         1.66           (2H, m)                                                         2.63           (2H, t)                                                         3.83           (3H, s)                                                         6.90-7.10      (1H, m)                                                         7.10-7.50      (6H, m)                                                  ______________________________________                                    

EXAMPLE 7 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-propylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 19)

Ethyl 2-chloro-6-fluorobenzimidate (3.02 g) and triethylamine (1.80 g) are dissolved in toluene (30 ml) and 2-chloro-4-propylbenzoyl chloride (3.30 g) is added dropwise thereto within a range of 5° C.-15° C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 1 hour. After cooling to room temperature, the reaction solution is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (1.80 g) and heated under reflux for 4 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 0.41 g of desired compound (refractive index: 1.5868).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.95           (3H, t)                                                         1.65           (2H, m)                                                         2.62           (2H, t)                                                         3.83           (3H, s)                                                         6.80-7.50      (6H, m)                                                  ______________________________________                                    

EXAMPLE 8 Preparation of 5-(4-butyl-2-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 29)

N-methyl-N-(phenylsulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.10 g), 4-butyl-2-chlorobenzonitrile (0.60 g) and anhydrous aluminum chloride (0.50 g) are added to o-dichlorobenzene (10 ml) and stirred at 120° C. for 1 hour. On completion of the reaction, chloroform (100 ml) is added and washed with dilute hydrochloric acid. After washing with water, the organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 0.70 g of compound (refractive index: 1.5667).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.75-1.12      (3H, m)                                                         1.15-2.00      (4H, m)                                                         2.65           (2H, t)                                                         3.85           (3H, s)                                                         6.83-7.60      (6H, m)                                                  ______________________________________                                    

EXAMPLE 9 Preparation of 5-(4-t-butyl-2-ethoxyphenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 35)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.60 g), 4-t-butyl-2-ethoxybenzonitrile (1.00 g), anhydrous aluminum chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.20 g of desired compound (melting point: 108.0°-111.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                1.15           (9H, s)                                                         1.36           (3H, t)                                                         3.87           (3H, s)                                                         4.10           (2H, q)                                                         6.83-7.58      (6H, m)                                                  ______________________________________                                    

EXAMPLE 10 Preparation of 3-(2-chlorophenyl)-5-(2-fluoro-5-hexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 42)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (2.06 g), 2-fluoro-5-hexylbenzonitrile (1.23 g), anhydrous aluminum chloride (0.88 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.60 g of desired compound (refractive index: 1.5779).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.87           (3H, t)                                                         1.00-1.90      (8H, m)                                                         2.62           (2H, t)                                                         3.87           (3H, d)                                                         6.90-8.00      (7H, m)                                                  ______________________________________                                    

EXAMPLE 11 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-fluoro-5-hexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 43)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (2.17 g), 2-fluoro-5-hexylbenzonitrile (1.23 4), anhydrous aluminum chloride (0.88 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.11 g of desired compound (refractive index: 1.5608).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.87           (3H, t)                                                         1.00-1.80      (8H, m)                                                         2.61           (2H, t)                                                         3.89           (3H, d)                                                         6.80-7.40      (6H, m)                                                  ______________________________________                                    

EXAMPLE 12 Preparation of 3-(2,6-difluorophenyl)-5-(2-fluoro-5-undecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 46)

A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (1.28 g), 2-fluoro-5-undecylbenzonitrile (1.09 g), anhydrous aluminum chloride (0.55 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.08 g of desired compound (melting point: 70.0°-73.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.88           (3H, t)                                                         1.10-1.80      (18H, m)                                                        2.63           (2H, t)                                                         3.93           (3H, d)                                                         6.90-7.60      (6H, m)                                                  ______________________________________                                    

EXAMPLE 13 Preparation of 3-(2-chlorophenyl)-5-(2-fluoro-5-undecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 47)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (1.27 g), 2-fluoro-5-undecylbenzonitrile (1.09 g), anhydrous aluminum chloride (0.55 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.85 g of desired compound (melting point: 35.0°-37.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.88           (3H, t)                                                         1.10-1.70      (18H, m)                                                        2.66           (2H, t)                                                         3.93           (3H, d)                                                         6.90-7.60      (6H, m)                                                         7.90-8.00      (1H, m)                                                  ______________________________________                                    

EXAMPLE 14 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-fluoro-5-undecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 48)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.34 g), 2-fluoro-5-undecylbenzonitrile (1.09 g), anhydrous aluminum chloride (0.55 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.04 g of desired compound (refractive index: 1.5419).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.87           (3H, t)                                                         1.10-1.80      (18H, m)                                                        2.63           (2H, t)                                                         3.94           (3H, d)                                                         6.90-7.60      (6H, m)                                                  ______________________________________                                    

EXAMPLE 15 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-dodecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 51)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 2-chloro-4-dodecylbenzonitrile (1.20 g), anhydrous aluminum chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.80 g of desired compound (refractive index: 1.5490).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.50-2.03      (23H, m)                                                        2.65           (2H, t)                                                         3.83           (3H, s)                                                         6.82-7.52      (6H, m)                                                  ______________________________________                                    

EXAMPLE 16 Preparation of 5-(4-butoxy-2-chlorophenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 64)

Ethyl 2-chlorobenzimidate (2.40 g) and triethylamine (1.20 g) are dissolved in toluene (100 ml) and 4-butoxy-2-chlorobenzoyl chloride (2.60 g) is added drop-wise thereto below 10° C. with stirring. It is stirred at room temperature for 2 hours and further heated under reflux for 2 hours. On completion of the reaction, the reaction solution is washed with saline, further washed with water and the organic layer is dried over anhydrous magnesium sulfate. The toluene layer is added with monomethyl hydrazine (1.50 g) and reacted at room temperature for 24 hours. On completion of the reaction, it is washed with dilute hydrochloric acid, further washed with water and the organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.00 g of desired compound (melting point: 60.0°-62.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.80-1.16      (3H, m)                                                         1.20-2.10      (4H, m)                                                         3.84           (3H, s)                                                         4.02           (2H, t)                                                         6.76-7.95      (6H, m)                                                         7.83-8.12      (1H, m)                                                  ______________________________________                                    

EXAMPLE 17 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(4-chloro-3-pentyloxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 68)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.10 g), 4-chloro-3-pentyloxybenzonitrile (0.70 g), anhydrous iron (III) chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.50 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.72-2.16      (9H, m)                                                         4.06           (3H, s)                                                         4.10           (2H, t)                                                         6.85-7.60      (6H, m)                                                  ______________________________________                                    

EXAMPLE 18 Preparation of 5-(4-chloro-3-octyloxyphenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 77)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (1.50 g), 4-chloro-3-octyloxybenzonitrile (1.30 g), anhydrous iron (III) chloride (0.80 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.80 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.65-2.13      (15H, m)                                                        4.07           (3H, s)                                                         4.13           (2H, t)                                                         6.92-7.66      (7H, m)                                                  ______________________________________                                    

EXAMPLE 19 Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-methoxyethoxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 87)

Ethyl 2-chlorobenzimidate (4.00 g) and triethylamine (2.60 g) are dissolved in toluene (20 ml) and 2-chloro-4-methoxyethoxybenzoyl chloride (4.20 g) is added dropwise thereto within a range of 5° C.-10° C. with stirring. It is stirred at room temperature for 1 hour and further heated under reflux for 30 minutes. After cooling to room temperature, the reaction solution is added with toluene (20 ml) and washed with dilute sulfuric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and stirred at room temperature for 4 hours. On completion of the reaction, the reaction mixture is washed with dilute sulfuric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.70 g of desired compound (refractive index: 1.5946).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.45           (3H, s)                                                         3.60-3.97      (4H, m)                                                         4.00           (3H, s)                                                         6.83-8.13      (7H, m)                                                  ______________________________________                                    

EXAMPLE 20 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-5-perfluorobutylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 116)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.70 g), 2-chloro-5-perfluorobutylbenzonitrile (1.75 g), anhydrous iron (III) chloride (0.73 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 130° C. for 2 hours. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.68 g of desired compound (refractive index: 1.5110).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.87           (3H, s)                                                         6.80-7.97      (6H, m)                                                  ______________________________________                                    

EXAMPLE 21 Preparation of 3-(2-chlorophenyl)-5-(2-chloro-5-perfluorohexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 119)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chlorobenzohydrazonoyl chloride (0.51 g), 2-chloro-5-perfluorohexylbenzonitrile (0.70 g), anhydrous aluminum chloride (0.20 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.15 g of desired compound (melting point: 70.0°-76.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.85           (3H, s)                                                         7.13-8.06      (7H, m)                                                  ______________________________________                                    

EXAMPLE 22 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-5-perfluorohexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 120)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.73 g), 2-chloro-5-perfluorohexylbenzonitrile (1.00 g), anhydrous iron (III) chloride (0.36 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.15 g of desired compound (melting point: 78.0°-82.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.86           (3H, s)                                                         6.86-7.86      (6H, m)                                                  ______________________________________                                    

EXAMPLE 23 Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-allyloxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 138).

Ethyl 2-chlorobenzimidate (2.60 g) and triethylamine (1.10 g) are dissolved in toluene (20 ml) and 2-chloro-4-allyloxybenzoyl chloride (2.20 g) is added dropwise thereto within a range of 5° C.-10° C. with stirring. It is stirred at room temperature for 1 hour and further heated under reflux for 30 minutes. After cooling to room temperature, the reaction solution is added with toluene (20 ml) and washed with dilute sulfuric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and stirred at room temperature for 5 hours. On completion of the reaction, the reaction mixture is washed with dilute sulfuric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound (refractive index: 1.6083).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.85           (3H, s)                                                         4.50-4.80      (2H, m)                                                         5.25-5.62      (2H, m)                                                         5.77-6.40      (1H, m)                                                         6.82-8.16      (7H, m)                                                  ______________________________________                                    

EXAMPLE 24 Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-propargyroxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 145)

Ethyl 2-chlorobenzimidate (3.00 g) and triethylamine (1.50 g) are dissolved in toluene (20 ml) and 2-chloro-4-propargyroxybenzoyl chloride (2.30 g) is added dropwise thereto within a range of 5° C.-10° C. with stirring. It is stirred at room temperature for 1 hour and further heated under reflux for 30 minutes. After cooling to room temperature, the reaction solution is added with toluene (20 ml) and washed with dilute sulfuric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and stirred at room temperature for 4 hours. On completion of the reaction, the reaction mixture is washed with dilute sulfuric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound (melting point: 103.0-105.0).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.47-2.71      (1H, m)                                                         3.83           (3H, s)                                                         4.75           (2H, d)                                                         6.83-8.20      (7H, m)                                                  ______________________________________                                    

EXAMPLE 25 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 4-fluoro-3-(4-trifluoromethoxyphenyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 157)

A mixture of N-methyl-N-(methanesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 4-fluoro-3-(4-trifluoromethoxyphenyl)benzonitrile (1.43 g), anhydrous iron (III) chloride (0.90 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, the reaction mixture is dissolved in ethylacetate (200 ml), washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.90 g of desired compound (melting point: 117.0°-119.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         6.80-7.90      (10H, m)                                                 ______________________________________                                    

EXAMPLE 26 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 2-chloro-4-(4-trifluoromethoxyphenyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 158)

A mixture of N-methyl-N-(methanesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 4-(4-trifluoromethoxyphenyl)benzonitrile (1.56 g), anhydrous iron (III) chloride (0.90 g) and chlorobenzene (20 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (300 ml), washed with dilute hydrochrolic acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.80 g of desired compound (refractive index: 1.5925).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.90           (3H, s)                                                         6.90-7.70      (10H, m)                                                 ______________________________________                                    

EXAMPLE 27 Preparation of 5- 3-chloro-4-(3,4-dichlorobenzyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 161)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 3-chloro-4-(3,4-dichlorobenzyl)benzonitrile (0.93 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (300 ml), washed with dilute hydrochrolic acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.64 g of desired compound (melting point: 179.0°-185.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.03           (3H, s)                                                         4.23           (2H, s)                                                         6.67-7.86      (9H, m)                                                  ______________________________________                                    

EXAMPLE 28 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(2-chloro-4-trifluoromethylphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 196)

To 30 ml of N,N-dimethylformamide are added 2-chloro-4-trifluoromethyl phenol (0.29 g) and potassium carbonate (0.25 g) and 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (0.60 g) is added thereto at room temperature with stirring, which is stirred at 120° C. for 1 hour. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with toluene. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.61 g of desired compound (melting point: 113.0°-114.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         5.30           (2H, s)                                                         6.87-8.10      (9H, m)                                                  ______________________________________                                    

EXAMPLE 29 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(2-fluoro-4-trifluoromethylphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 197)

To 100 ml of N,N-dimethylformamide are added 5-(3-chloro-4-chloromethylphenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (1.60 g) and potassium carbonate (0.60 g) and 2-fluoro-4-trifluoromethyl phenol (0.80 g) is added thereto at room temperature with stirring, which is stirred at 70° C. for 3 hours. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.62 g of desired compound (refractive index: 1.6010).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         5.31           (2H, s)                                                         6.75-8.00      (9H, m)                                                  ______________________________________                                    

EXAMPLE 30 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(4-trifluoromethylphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 199)

To 30 ml of N,N-dimethylformamide are added 4-trifluoromethyl phenol (0.77 g) and potassium carbonate (0.72 g) and 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (1.60 g) is added thereto at room temperature with stirring, which is stirred at 120° C. for 1 hour. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with toluene. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.50 g of desired compound (refractive index: 1.5961).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.08           (3H, s)                                                         5.23           (2H, s)                                                         6.87-7.47      (7H, m)                                                         7.65           (2H, s)                                                         7.83           (1H, s)                                                  ______________________________________                                    

EXAMPLE 31 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(4-trifluoromethoxyphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 201)

To 30 ml of N,N-dimethylformamide are added 4-trifluoromethoxy phenol (0.33 g) and potassium carbonate (0.25 g) and 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (0.70 g) is added thereto at room temperature with stirring, which is stirred at 120° C. for 1 hour. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with toluene. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.83 g of desired compound (refractive index: 1.5701).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.08           (3H, s)                                                         5.19           (2H, s)                                                         6.70-7.40      (7H, m)                                                         7.65           (1H, s)                                                  ______________________________________                                    

EXAMPLE 32 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-phenoxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 241)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (3.30 g), 2-chloro-4-phenoxybenzonitrile (2.30 g), anhydrous iron (III) chloride (1.60 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochrolic acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.15 g of desired compound (melting point: 135.0°-140.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.91           (3H, s)                                                         6.90-8.06      (11H, m)                                                 ______________________________________                                    

EXAMPLE 33 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)-phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 259)

Ethyl 2-chloro-6-fluorobenzimidate (1.80 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)benzoyl chloride (3.70 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100° C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The reaction solution is added with monomethyl hydrazine (0.80 g) and stirred at 100° C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 1.50 g of desired compound (melting point: 67.0-72.0).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.05           (3H, s)                                                         6.40-7.95      (8H, m)                                                  ______________________________________                                    

EXAMPLE 34 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(2-chloro-4-trifluoromethylbenzyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 273)

To 20 ml of N,N-dimethylformamide are added 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole (0.70 g) and potassium carbonate (0.31 g) and 2-chloro-4-trifluoromethylbenzyl chloride (0.50 g) is added thereto at room temperature with stirring, which is stirred at 120° C. for 5 hours. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.80 g of desired compound (melting point: 156.0°-159.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.05           (3H, s)                                                         5.30           (2H, s)                                                         6.80-7.95      (9H, m)                                                  ______________________________________                                    

EXAMPLE 35 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(2-fluoro-4-trifluoromethylbenzyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 274)

To 20 ml of N,N-dimethylformamide are added 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole (0.90 g) and potassium carbonate (0.40 g) and 2-fluoro-4-trifluoromethylbenzyl chloride (0.50 g) is added thereto at room temperature with stirring, which is stirred at 120° C. for 5 hours. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.60 g of desired compound (melting point: 109.0°-111.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.00           (3H, s)                                                         5.25           (2H, s)                                                         6.80-7.90      (9H, m)                                                  ______________________________________                                    

EXAMPLE 36 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(4-trifluoromethylbenxyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 275)

Ethyl 2-chloro-6-fluorobenzimidate (2.40 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethylbenzyloxy)benzoyl chloride (3.50 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100° C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100° C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.20 g of desired compound (melting point: 43.0°-47.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.05           (3H, s)                                                         5.25           (2H, s)                                                         6.90-7.95      (10H, m)                                                 ______________________________________                                    

EXAMPLE 37 Preparation of 5- 3-chloro-4-(4-trifluoromethylbenzyloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 276)

Ethyl 2,6-difluorobenzimidate (2.20 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethylbenzyloxy)benzoyl chloride (3.50 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100° C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100° C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.00 g of desired compound (melting point: 171.0°-177.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.00           (3H, s)                                                         5.20           (2H, s)                                                         6.65-7.90      (10H, m)                                                 ______________________________________                                    

EXAMPLE 38 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(4-trifluoromethoxybenzyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 277)

Ethyl 2-chloro-6-fluorobenzimidate (2.40 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethoxybenzyloxy)benzoyl chloride (3.70 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100° C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100° C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.50 g of desired compound (refractive index: 1.5680).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.00           (3H, s)                                                         5.10           (2H, s)                                                         6.85-7.90      (10H, m)                                                 ______________________________________                                    

EXAMPLE 39 Preparation of 5- 3-chloro-4-(4-trifluoromethoxybenzyloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 278)

Ethyl 2,6-difluorobenzimidate (2.20 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethoxybenzyloxy)benzoyl chloride (3.70 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100° C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100° C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.50 g of desired compound (melting point: 132.0°-136.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.00           (3H, s)                                                         5.10           (2H, s)                                                         6.70-8.20      (10H, m)                                                 ______________________________________                                    

EXAMPLE 40 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 2-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 317)

3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (0.50 g) is dissolved in 1,2-dimethoxyethane (20 ml) and cooled to 0° C., to which is added sodium hydride (60%, 0.07 g) and the reaction mixture is stirred for 15 minutes. Then, a solution of 2,3-dichloro-5-trifluoromethyl pyridine (0.34 g) in 1,2-dimethoxyethane (10 ml) is added dropwise and stirred for 3 hours. On completion of the reaction, the reaction solution is warmed to room temperature and poured into water and extracted with ether. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.62 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.83           (3H, s)                                                         5.50           (2H, s)                                                         6.83-8.37      (8H, m)                                                  ______________________________________                                    

EXAMPLE 41 Preparation of 5- 3-chloro-4-(3,5-dichloropyridine-2-yloxymethyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 330)

Sodium hydride (60%, 0.12 g) is added to 1,2-dimethoxyethane (50 ml) and a solution of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (1.00 g) in 1,2-dimethoxyethane (20 ml) is added dropwise thereto at -5° C. and stirred for 20 minutes. The reaction solution is added dropwise with a solution of 2,3,5-trichloropyridine (0.60 g) in 1,2-dimethoxyethane (20 ml) at -5° C. for 10 minutes with stirring. The reaction mixture is warmed to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.40 g of desired compound (melting point: 153.0°-155.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.06           (3H, s)                                                         5.48           (2H, s)                                                         6.75-7.30      (3H, m)                                                         7.50-8.00      (5H, m)                                                  ______________________________________                                    

EXAMPLE 42 Preparation of 5- 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 332)

Sodium hydride (60%, 0.16 g) is added to 1,2-dimethoxyethane (50 ml) and a solution of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (1.20 g) in 1,2-dimethoxyethane (20 ml) is added dropwise thereto at -5° C. with stirring. To the reaction solution is added dropwise a solution of 2,3-dichloro-5-trifluoromethyl pyridine (0.80 g) in 1,2-dimethoxyethane (20 ml) at -5° C. for 10 minutes, which is further stirred for 15 minutes. On completion of the reaction, the reaction solution is warmed to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.10 g of desired compound (melting point: 47.0°-49.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.06           (3H, s)                                                         5.57           (2H, s)                                                         6.84-7.50      (3H, m)                                                         7.60-7.75      (4H, m)                                                         8.30           (1H, s)                                                  ______________________________________                                    

EXAMPLE 43 Preparation of 5- 3-chloro-4-(5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 334)

Sodium hydride (60%, 0.12 g) is added to 1,2-dimethoxyethane (50 ml) and a solution of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (1.00 g) in 1,2-dimethoxyethane (20 ml) is added dropwise thereto at -5° C., which is stirred for 15 minutes. To the reaction solution is added dropwise a solution of 2-chloro-5-trifluoromethyl pyridine (0.60 g) in 1,2-dimethoxyethane (20 ml) at -5° C., which is stirred for 15 minutes. The reaction mixture is warmed to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.80 g of desired compound (refractive index: 1.5879).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.06           (3H, s)                                                         5.57           (2H, s)                                                         6.75-8.42      (9H, m)                                                  ______________________________________                                    

EXAMPLE 44 Preparation of 5- 4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 377)

A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (0.90 g), 4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.30 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.02           (3H, s)                                                         6.64-7.98      (8H, m)                                                         8.20-8.38      (1H, m)                                                  ______________________________________                                    

EXAMPLE 45 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 378)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.40 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.12           (3H, s)                                                         6.92-8.11      (8H, m)                                                         8.33-8.50      (1H, m)                                                  ______________________________________                                    

EXAMPLE 46 Preparation of 3-(2-chlorophenyl)-5- 2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 389)

A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (2.05 g), 2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.88 g), anhydrous iron (III) chloride (1.07 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.87 g of desired compound (melting point: 104.0°-108.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.88           (3H, s)                                                         6.90-8.40      (10H, m)                                                 ______________________________________                                    

EXAMPLE 47 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 390)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (2.25 g), 2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.88 g), anhydrous iron (III) chloride (1.07 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.54 g of desired compound (melting point: 139.0°-141.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.90           (3H, s)                                                         6.90-8.40      (9H, m)                                                  ______________________________________                                    

EXAMPLE 48 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 401)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.00 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         6.73-7.52      (3H, m)                                                         7.80           (2H, s)                                                         7.97-8.10      (1H, m)                                                         8.12-8.26      (1H, m)                                                  ______________________________________                                    

EXAMPLE 49 Preparation of 5- 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 409)

A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (0.90 g), 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.70 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         6.72-8.06      (7H, m)                                                         8.14-8.30      (1H, m)                                                  ______________________________________                                    

EXAMPLE 50 Preparation of 5- 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 410)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.90 g), 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.80 g), anhydrous iron (III) chloride (0.40 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.16           (3H, s)                                                         6.92-8.16      (7H, m)                                                         8.24-8.40      (1H, m)                                                  ______________________________________                                    

EXAMPLE 51 Preparation of 5- 3-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 412)

A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (1.72 g), 3-chloro-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.50 g), anhydrous iron (III) chloride (0.85 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (200 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent and washed with hexane to give 1.25 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.11           (3H, s)                                                         6.80-8.40      (9H, m)                                                  ______________________________________                                    

EXAMPLE 52 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 413)

To N,N-dimethylformamide (50 ml) are added 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole (3.04 g), 2-chloro-5-trifluoromethyl pyridine (1.70 g) and potassium carbonate (1.40 g), which is heated at 120° C. for 2 hours with stirring. After cooling to room temperature, the reaction solution is poured into water and extracted with ethyl acetate, and the layer is washed with water and dried over anhydrous magnesium sulfate. After the concentration under reduced pressure, the crude solid is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 3.30 g of desired compound (melting point: 116.0°-117.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         6.90-8.30      (9H, m)                                                  ______________________________________                                    

EXAMPLE 53 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-perfluorobutyl-4-(3-chloro-5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 451)

3-(2-chloro-6-fluorophenyl)-1-methyl-5-(3-perfluorobutyl-4-hydroxymethylphenyl)-1H-1,2,4-triazole (1.00 g) is dissolved in 1,2-dimethoxyethane (20 ml) and cooled to 0° C. It is added with sodium hydride (60%, 0.08 g) and stirred for 30 minutes. A solution of 2,3-dichloro-5-trifluoromethyl pyridine (0.44 g) in 1,2-dimethoxyethane (10 ml) is added dropwise thereto and stirred for 3 hours. On completion of the reaction, the reaction solution is warmed to room temperature, poured into water and extracted with ether. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.00 g of desired compound (melting point: 123.0°-127.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.08           (3H, s)                                                         5.73           (2H, s)                                                         6.85-7.40      (4H, m)                                                         7.75-8.27      (4H, m)                                                  ______________________________________                                    

EXAMPLE 54 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-perfluorobutyl-4-(5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 453)

3-(2-chloro-6-fluorophenyl)-1-methyl-5-(3-perfluorobutyl-4-hydroxymethylphenyl)-1H-1,2,4-triazole (1.00 g) is dissolved in 1,2-dimethoxyethane (20 ml) and cooled to 0° C. It is added with sodium hydride (60%, 0.08 g) and stirred for 30 minutes. A solution of 2-chloro-5-trifluoromethyl pyridine (0.36 g) in 1,2-dimethoxyethane (10 ml) is added dropwise thereto and stirred for 5 hours. On completion of the reaction, the reaction solution is warmed to room temperature, poured into water and extracted with ether. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.70 g of desired compound (refractive index: 1.5020).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.12           (3H, s)                                                         5.70           (2H, s)                                                         6.80-8.53      (9H, m)                                                  ______________________________________                                    

EXAMPLE 55 Preparation of 3-(2-chloro-6-fluorophenyl)-1-methyl-5- 3-methyl-4-(4-trifluoromethoxyphenyl)phenyl!-1H-1,2,4-triazole (Compound No. 457)

A mixture of N-methyl-N-(methanesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 3-methyl-4-(4-trifluoromethoxyphenyl)benzonitrile (1.42 g), anhydrous iron (III) chloride (0.90 g) and chlorobenzene (10 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent and washed with hexane to give 1.64 g of desired compound (melting point: 117.0°-122.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.23           (3H, s)                                                         4.10           (3H, s)                                                         6.90-7.70      (10H, m)                                                 ______________________________________                                    

EXAMPLE 56 Preparation of 3-(2-chlorophenyl)-1-methyl-5- 4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1H-1,2,4-triazole (Compound No. 509)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-benzohydrazonoyl chloride (1.1 g), 4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.00 g), anhydrous iron (III) chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.50 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.26           (3H, s)                                                         4.07           (3H, s)                                                         6.95-8.16      (9H, m)                                                         8.36-8.52      (1H, m)                                                  ______________________________________                                    

EXAMPLE 57 Preparation of 3-(2-chloro-6-fluorophenyl)-1-methyl-5- 4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1H-1,2,4-triazole (Compound No. 510)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.10 g), 4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.24           (3H, s)                                                         4.12           (3H, s)                                                         6.85-8.07      (8H, m)                                                         8.36-8.52      (1H, m)                                                  ______________________________________                                    

EXAMPLE 58 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1H-1,2,4-triazole (Compound No. 516)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.50 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.85           (3H, s)                                                         4.14           (3H, s)                                                         6.92-8.08      (8H, m)                                                         8.35-8.52      (1H, m)                                                  ______________________________________                                    

EXAMPLE 59 Preparation of 3-(2,6-difluorophenyl)-5- 4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 517)

A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (0.70 g), 4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.80 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.30 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.84           (3H, s)                                                         4.10           (3H, s)                                                         6.75-8.10      (8H, m)                                                         8.30-8.47      (1H, m)                                                  ______________________________________                                    

EXAMPLE 60 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-5-methoxyphenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 523)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.90 g), 3-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-5-methoxybenzonitrile (0.80 g), anhydrous iron (III) chloride (0.80 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.92           (3H, s)                                                         4.12           (3H, s)                                                         6.85-7.53      (6H, m)                                                         7.96-8.06      (1H, m)                                                         8.23-8.40      (1H, m)                                                  ______________________________________                                    

EXAMPLE 61 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 3-methoxy-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1-1,2,4-triazole (Compound No. 524)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (3.75 g), 3-methoxy-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (3.03 g), anhydrous iron (III) chloride (1.70 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent and washed with hexane to give 2.80 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.97           (3H, s)                                                         3.07           (3H, s)                                                         6.90-8.30      (9H, m)                                                  ______________________________________                                    

EXAMPLE 62 Preparation of 3-(2-chloro-6-fluorophenyl)-5- 4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-3-methoxyphenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 526)

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.90 g), 4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-3-methoxybenzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140° C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.81           (3H, s) Z                                                       4.13           (3H, s)                                                         6.90-7.60      (6H, m)                                                         7.93-8.06      (1H, m)                                                         8.16-8.30      (1H, m)                                                  ______________________________________                                    

EXAMPLE 63 Preparation of 5-(2-chloro-4-hexylphenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 40)

A mixture of N-methyl-N-phenylsulfonyl-2-chlorobenzamidrazone (3.24 g) and 2-chloro-4-hexylbenzoyl chloride (3.37 g) is stirred at an oil bath temperature of 170°-180° C. for 4 hours. After cooling to room temperature, it is added with ethyl acetate and the organic layer is washed with water. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.85 g of desired compound (refractive index: 1.5830).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                0.90           (3H, t)                                                         1.00-1.90      (8H, m)                                                         2.67           (2H, t)                                                         3.87           (3H, s)                                                         7.10-7.60      (6H, m)                                                         7.90-8.05      (1H, m)                                                  ______________________________________                                    

Reference Example 1 Preparation of N-methyl-N-(benzenesulfonyl)-2-chlorobenzamidorazone

N-methyl-N-(benzenesulfonyl)-2-chlorobenzhydrazonoyl chloride (17.2 g) is dissolved in N,N-dimethylformamide (100 ml) and stirred at 60°-70° C. for 3 hours while introducing ammonia gas thereinto. After cooling, it is dissolved in 500 ml of ethyl acetate and washed with water. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure and the crude solid is washed with hexane to give 15.4 g of desired compound (melting point: 94.0°-96.0° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.75           (3H, s)                                                         5.80           (2H, s)                                                         7.10-8.00      (9H, m)                                                  ______________________________________                                    

Reference Example 2 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methylphenyl)-1-methyl-1H-1,2,4-triazole

A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (7.50 g), 3-chloro-4-methylbenzonitrile (3.33 g), anhydrous aluminum chloride (3.00 g) and o-dichlorobenzene (20 ml) is stirred at an oil bath temperature of 140° C. for 1 hour. After cooling, it is washed with saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 3.70 g of desired compound.

Reference Example 3 Preparation of 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1,2,4-triazole

To carbon tetrachloride (50 ml) are added 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methylphenyl)-1-methyl-1H-1,2,4-triazole (3.37 g), N-bromosuccinicimide (2.14 g) and azobisisobutyronitrile (30 mg), which are heated under reflux for 1 hour with stirring. After cooling of the reaction mixture, insoluble matter is filtered off, and the filtrate is concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 2.51 g of desired compound (melting point 124.0°-126.0° C.).

Reference Example 4 Preparation of 5-(4-acetoxymethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole

To N,N-dimethylformamide (200 ml) are added 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (24.3 g) and potassium acetate (29.0 g), which are stirred at 130° C. for 3 hours. The reaction mixture is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 11.8 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                2.13           (3H, s)                                                         4.07           (3H, s)                                                         5.24           (2H, s)                                                         6.90-7.85      (6H, m)                                                  ______________________________________                                    

Reference Example 5 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole

5-(4-acetoxymethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (11.1 g) is dissolved in a mixed solvent of ethanol (50 ml) and water (20 ml), added with sodium hydroxide (2.3 g) and heated under reflux for 1 hour with stirring. After cooling to room temperature, the reaction mixture is added with ethyl acetate and washed with water. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain crude solid. The crude solid is washed with mixed solvent of hexane-ethanol to give 6.7 g of desired compound (melting point: 111°-113° C.).

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                3.50           (1H, t)                                                         4.05           (3H, s)                                                         4.75           (2H, d)                                                         6.95-7.70      (6H, m)                                                  ______________________________________                                    

Reference Example 6 Preparation of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole

To o-dichlorobenzene (200 ml) are added 3-chloro-4-methoxybenzonitrile (40.3 g) and anhydrous iron (III) chloride (42.2 g), which are heated at 120° C. with stirring. To this mixture is added dropwise a solution of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (62.2 g) in o-dichlorobenzene (300 ml) at 120° C. for 30 minutes with stirring, which are further stirred at 120° C. for 3 hours. After cooling to room temperature, the reaction mixture is poured into a large amount of water and extracted with chloroform. The organic layer is added with aqueous solution of 10% NaOH (200 ml) and aqueous solution of 25% ammonia (200 ml) and stirred at 50° C. for 1 hour. After cooling to room temperature, the organic layer is washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure to give 70.5 g of a crude product of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methoxyphenyl)-1-methyl-1H-1,2,4-triazole.

To benzene (300 ml) are added the crude product of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methoxyphenyl)-1-methyl-1H-1,2,4-triazole (70.5 g) and anhydrous aluminum chloride (80.0 g), which are heated under reflux for 3 hours with stirring. After cooling to room temperature, the reaction mixture is poured into ice water and extracted with toluene. The organic layer is washed with water, extracted with aqueous solution of 20% NaOH, and the aqueous layer is acidified by adding a concentrated sulfuric acid little by little while cooling with ice and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 64.2 g of desired compound.

NMR data (60 MHz, CDCl₃ solvent, δ value: ppm)

    ______________________________________                                                4.10           (3H, s)                                                         7.00-7.90      (6H, m)                                                         10.85          (1H, s)                                                  ______________________________________                                    

The insecticide and acaricide according to the invention contain the triazole derivative shown by the general formula I! as an active ingredient.

When the compounds according to the invention are used in the insecticide and acaricide, these compounds themselves may be used alone, or may be compounded with a carrier, a surfactant, a dispersing agent, an adjuvant or the like, which is usually used in the formulation, to form dust, wettable powder, emulsion, fine powder, granulate or the like. As the carrier used in the formulation, mention may be made of a solid carrier such as zeeklite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium hydroxide, quartz sand, ammonium sulfate, urea or the like; and a liquid carrier such as isopropyl alcohol, xylene, cyclohexane, methylnaphthalene or the like. As the surfactant and dispersing agent, mention may be made of a metal salt of alkylbenzene sulfonic acid, a metal salt of dinaphthylmethane disulfonic acid, a salt of sulfuric acid ester of alcohol, alkylarylsulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monoalkylate and the like. As the adjuvant, mention may be made of carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. In use, the active ingredient is sprayed by diluting to a proper concentration or directly applied.

The insecticide and acaricide according to the invention may be used by spraying onto stem and leaves, by applying to soil, by applying to a nursery box, by spraying onto water surface or the like. The compounding ratio of the active ingredient may properly be selected, if necessary, but in case of the dust or granulate, it may properly be selected from a range of 0.05-20% (by weight), preferably 0.1%-10% (by weight). In case of the emulsion or wettable powder, it is suitable within a range of 0.5-80% (by weight). Preferably, it may properly be selected within a range of 1-60% (by weight).

The amount of the insecticide or acaricide according to the invention applied is dependent upon the kind of the compound used, injurious insect to be controlled, tendency and degree of insect injury, environmental condition, kind of formulation used and the like. When it is directly used as dust or granulate, the amount of the active ingredient is properly selected within a range of 0.05 g-5 kg, preferably 0.1 g-1 kg per 10 are. Furthermore, when it is used in form of a liquid as emulsion or wettable powder, the amount is properly selected within a range of 0.1-5,000 ppm, preferably 1-1,000 ppm. And also, the insecticide and acaricide according to the invention may be used by mixing with other insecticide, fungicide, fertilizer and plant growth regulator.

Then, the formulation will concretely be described with respect to typical examples. In this case, the kind of the compounds and additives and the compounding ratio are not limited to these examples and may be varied within wide ranges. Moreover, % is by weight otherwise specified.

Formulation Example 1

Emulsion

An emulsion is prepared by uniformly dissolving 30% of the compound (41), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzene sulfonate and 35% of methylnaphthaline.

Formulation Example 2

Wettable powder

A wettable powder is prepared by uniformly mixing and pulverizing 40% of the compound (389), 15% of diatomaceous earth, 15% of clay, 25% of white carbon, 2% of sodium dinaphthylmethane disulfonate and 3% of sodium lignin sulfonate.

Formulation Example 3

Dust

A dust is prepared by uniformly mixing and pulverizing 2% of the compound (116), 5% of diatomaceous earth and 93% of clay.

Formulation Example 4

Granulate

5% of the compound (41), 2% of sodium salt of lauryl alcohol sulfuric acid ester, 5% of sodium lignin sulfonate, 2% of carboxymethyl cellulose and 86% of clay are mixed and pulverized uniformly. Then, 100 parts by weight of this mixture is added and kneaded with 20 parts by weight of water and shaped into granulates of 14-32 mesh through an extrusion type granulating machine and dried to prepare granulates.

EFFECT OF THE INVENTION!

The triazole derivatives according to the invention are effective for the control of planthoppers such as brown planthopper, white-backed planthopper, small brown planthopper and the like; leafhoppers such as green rice leafhopper, tea green leafhopper and the like; aphids such as cotton aphid, green peach aphid, cabbage aphid and the like; whiteflies such as greenhouse whitefly and the like; hemipteran injurious insects such as scales, e.g. mulberry scale or the like and bugs, e.g. corbett rice bug or the like; lepidopteran injurious insects such as diamond-back moth, beet armyworm, common cutworm and the like; dipteran injurious insects such as house fly, mosquito and the like; elytron injurious insects such as rice plant weevil, azuki bean weevil, cucurbit leaf beetle and the like; orthopteran injurious insects such as American cockroach, German cockroach and the like; and mites such as two-spotted spider mite, Kanzawa spider mite, citrus red mite and the like. Especially, they have a very excellent controlling effect against mites such as two-spotted spider mite, Kanzawa spider mite, citrus red mite and the like; and aphids such as cotton aphid, green peach aphid, cabbage aphid and the like.

The effect of the compound according to the invention will be described with respect to the following test examples. Moreover, compounds shown by chemical formula 3 in JP-A-56-154464 as comparative chemicals a-b and compounds shown in Technical Report RD278004 as comparative chemicals c-d are used in the same formulation as in the test compounds.

Comparative chemical a: 3,5-bis(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole

Comparative chemical b: 3-(2-chlorophenyl)-1-methyl-5-(3-methylphenyl)-1H-1,2,4-triazole

Comparative chemical c: 3-(2-chlorophenyl)-1-methyl-5-(3-chloro-2-methylphenyl)-1H-1,2,4-triazole

Comparative chemical d: 3-(2-chloro-6-fluorophenyl)-1-methyl-5-(2,4-dichlorophenyl)-1H-1,2,4-triazole

Test Example 1

Acaricidal test for two-spotted spider mite

The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 500 ppm. In the resulting diluted wettable powder are immersed soy bean seedlings previously inoculated with adults of two-spotted spider mite and then dried in air. After the treatment, the soy bean seedlings are placed in a thermostatic chamber of 25° C. for 14 days and then the number of living adults is counted to calculate the percentage of control efficiency according to a calculation formula (1). The control efficiency is evaluated according to a standard of Table 3. The results are shown in Table 4. Moreover, the test is carried out by double series. ##EQU1##

                  TABLE 3                                                          ______________________________________                                         Control efficiency    Evaluation                                               ______________________________________                                         control efficiency of not less than 90%                                                              A                                                        control efficiency of not less than 70%                                                              B                                                        but less than 90%                                                              control efficiency of not less than 50%                                                              C                                                        but less than 70%                                                              control efficiency of less than 50%                                                                  D                                                        ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                                Compound                                                                       No.     Evaluation                                                      ______________________________________                                                 1      A                                                                       2      A                                                                       5      A                                                                       6      A                                                                       15     A                                                                       16     B                                                                       18     B                                                                       19     B                                                                       24     B                                                                       28     B                                                                       29     A                                                                       34     B                                                                       40     A                                                                       41     A                                                                       44     A                                                                       47     A                                                                       48     A                                                                       50     A                                                                       65     B                                                                       66     A                                                                       68     B                                                                       72     B                                                                       73     B                                                                       74     A                                                                       76     A                                                                       77     A                                                                       78     A                                                                       87     A                                                                      118     A                                                                      119     A                                                                      120     A                                                                      121     B                                                                      123     A                                                                      138     A                                                                      145     A                                                                      157     A                                                                      158     A                                                                      161     A                                                                      196     A                                                                      197     A                                                                      199     A                                                                      201     A                                                                      241     A                                                                      267     A                                                                      268     A                                                                      269     A                                                                      273     A                                                                      274     A                                                                      275     A                                                                      276     A                                                                      277     A                                                                      278     A                                                                      313     B                                                                      317     A                                                                      319     A                                                                      320     A                                                                      321     A                                                                      322     A                                                                      330     A                                                                      332     A                                                                      334     A                                                                      338     A                                                                      345     B                                                                      373     A                                                                      374     A                                                                      376     A                                                                      377     A                                                                      378     A                                                                      389     A                                                                      390     B                                                                      391     A                                                                      395     A                                                                      400     A                                                                      401     A                                                                      403     A                                                                      404     A                                                                      406     A                                                                      409     A                                                                      410     A                                                                      412     A                                                                      413     A                                                                      419     A                                                                      451     B                                                                      453     B                                                                      456     A                                                                      457     A                                                                      489     A                                                                      496     A                                                                      497     A                                                                      498     A                                                                      508     A                                                                      509     A                                                                      510     A                                                                      511     A                                                                      516     A                                                                      517     A                                                                      522     A                                                                      523     A                                                                      524     A                                                                      526     A                                                                      531     B                                                                      Comparative                                                                            D                                                                      chemical b                                                                     Comparative                                                                            D                                                                      chemical c                                                                     Comparative                                                                            D                                                                      chemical d                                                              ______________________________________                                    

Test Example 2

Insecticidal test for diamond-back moth

The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 500 ppm. Cabbage leaves are immersed in the resulting diluted solution, dried in air and then placed in a vinyl chloride cup. Ten larvae of diamond-back moth are released in the cup and thereafter a cover is placed thereon. Then, the cup is placed in a thermostatic chamber of 25° C. for 6 days, and the number of larvae died is counted to calculate the percentage of mortality according to a calculation formula (2). The mortality is evaluated according to a standard of Table 5. The results are shown in Table 6. Moreover, the test is carried out by double series. ##EQU2##

                  TABLE 4                                                          ______________________________________                                         Mortality          Evaluation                                                  ______________________________________                                         mortality of not less than 90%                                                                    A                                                           mortality of not less than 70%                                                                    B                                                           but less than 90%                                                              mortality of not less than 50%                                                                    C                                                           but less than 70%                                                              mortality of less than 50%                                                                        D                                                           ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                                Compound                                                                       No.     Evaluation                                                      ______________________________________                                                 51     A                                                                       78     A                                                                      116     A                                                                      118     A                                                                      157     A                                                                      158     A                                                                      161     A                                                                      196     A                                                                      197     A                                                                      199     A                                                                      276     A                                                                      317     A                                                                      319     A                                                                      320     A                                                                      321     A                                                                      322     A                                                                      330     A                                                                      332     A                                                                      334     A                                                                      338     A                                                                      376     A                                                                      391     A                                                                      409     A                                                                      413     A                                                                      419     A                                                                      456     A                                                                      457     A                                                                      496     A                                                                      497     A                                                                      498     A                                                                      514     A                                                                      524     A                                                                      526     A                                                                      Comparative                                                                            D                                                                      chemical a                                                                     Comparative                                                                            D                                                                      chemical c                                                                     Comparative                                                                            D                                                                      chemical d                                                              ______________________________________                                    

Test Example 3

Insecticidal test for brown planthopper

The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 500 ppm. In the resulting diluted wettable powder are immersed rice stems and leaves, which are then dried in air and placed in a test tube. In the test tube are released 10 larvae of brown planthopper and then the opening of the test tube is plugged with absorbent wadding. Thereafter, the test tube is placed in a thermostatic chamber of 25° C. for 6 days and then the number of larvae died is counted to calculate the percentage of mortality according to the calculation formula (2). The mortality is evaluated according to a standard of Table 5. The results are shown in Table 7. Moreover, the test is carried out by double series.

                  TABLE 7                                                          ______________________________________                                                Compound                                                                       No.     Evaluation                                                      ______________________________________                                                 2      A                                                                       78     B                                                                      116     A                                                                      311     B                                                                      378     B                                                                      395     B                                                                      517     A                                                                      524     A                                                                      Comparative                                                                            D                                                                      chemical a                                                                     Comparative                                                                            C                                                                      chemical b                                                                     Comparative                                                                            D                                                                      chemical d                                                              ______________________________________                                    

Test Example 4

Insecticidal test for cotton aphid

The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 100 ppm. In the resulting diluted wettable powder are immersed cucumber seedlings previously inoculated with larvae of cotton aphid and then dried in air. After the treatment, the cucumber seedlings are placed in a thermostatic chamber of 25° C. for 3 days and then the number of larvae died is counted to calculate the percentage of mortality according to the calculation formula (2). The mortality is evaluated according to a standard of Table 5. The results are shown in Table 8. Moreover, the test is carried out by double series.

                  TABLE 8                                                          ______________________________________                                                Compound                                                                       No.     Evaluation                                                      ______________________________________                                                 1      B                                                                       2      A                                                                       4      A                                                                       8      B                                                                       15     A                                                                       16     A                                                                       18     A                                                                       19     A                                                                       24     A                                                                       28     A                                                                       29     A                                                                       36     A                                                                       37     A                                                                       38     A                                                                       40     A                                                                       41     A                                                                       42     A                                                                       43     A                                                                       44     A                                                                       51     A                                                                       63     B                                                                       64     A                                                                       65     A                                                                       66     A                                                                       68     A                                                                       72     A                                                                       74     A                                                                       76     A                                                                       77     A                                                                       78     A                                                                       87     A                                                                      118     A                                                                      121     A                                                                      123     A                                                                      138     A                                                                      145     A                                                                      157     A                                                                      158     A                                                                      161     A                                                                      201     A                                                                      267     A                                                                      274     B                                                                      277     A                                                                      313     A                                                                      317     A                                                                      319     A                                                                      320     A                                                                      321     A                                                                      322     A                                                                      332     A                                                                      334     A                                                                      338     A                                                                      374     A                                                                      376     A                                                                      377     A                                                                      378     A                                                                      389     A                                                                      390     A                                                                      391     A                                                                      395     A                                                                      404     B                                                                      412     A                                                                      413     A                                                                      419     A                                                                      456     A                                                                      457     A                                                                      480     A                                                                      496     A                                                                      497     A                                                                      509     A                                                                      510     A                                                                      511     A                                                                      513     A                                                                      516     A                                                                      517     A                                                                      524     A                                                                      526     A                                                                      531     A                                                               ______________________________________                                     

We claim:
 1. A triazole derivative represented by the following formula: ##STR406## wherein R¹ is an alkyl (C1-C6) group, X is a hydrogen atom, a halogen atom, an alkyl (C1-C6) group, an alkoxy (C1-C6) group, an alkylthio (C1-C6) group, a nitro group or a cyano group, n is an integer of 1-5 provided that when n is 2 or more, X is the same or a different combination, Y' is a halogen atom, an alkyl (C1-C6) group, an alkoxy (C1-C6) group, a haloalkyl (C1-C6) group, a haloalkoxy (C1-C6) group, m' is an integer of 1-4 provided that when m' is 2 or more, Y' is the same or a different combination, A is an oxygen atom, a sulfur atom, an alkylene (C1-C4) group, an alkyleneoxy (C1-C4) group, an oxyalkylene (C1-C4) group, an alkyleneoxy (C1-C4) alkylene (C1-C4) group, an alkylenethio (C1-C4) group, a thioalkylene (C1-C4) group, a vinylene group or an ethylene group, k is 0 or 1, R² is a hydrogen atom, a halogen atom, an alkyl (C1-C6) group, an alkoxy (C1-C6) group, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-5 provided that when j is 2 or more, R² is the same or a different combination.
 2. A triazole derivative according to claim 1 wherein R¹ is an alkyl (C1-C6) group, X is a hydrogen atom or a halogen atom, n is an integer of 1-5 provided that when n is 2 or more, X is the same or a different combination, Y' is a halogen atom, an alkyl (C1-C6) group, an alkoxy (C1-C6) group, a haloalkyl (C1-C6) group or a haloalkoxy (C1-C6) group, m' is an integer of 1-4 provided that when m' is 2 or more, Y' is the same or a different combination, A is an oxygen atom, an alkylene (C1-C2) group, an alkyleneoxy (C1-C2) group or an oxyalkylene (C1-C2) group, k is 0 or 1, R² is a hydrogen atom, a halogen atom, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-5 provided that when j is 2 or more, R² is the same or a different combination.
 3. A triazole derivative according to claim 2, wherein R¹ is a methyl group, X is a halogen atom, n is 1 or 2 provided that when n is 2, X is the same or a different combination, Y' is a halogen atom, an alkyl (C1-C6) group, an alkoxy (C1-C6) group, a haloalkyl (C1-C6) group or a haloalkoxy (C1-C6) group, m' is an integer of 1 or 2 provided that when m' is 2, Y' is the same or a different combination, A is an oxygen atom, an alkylene (C1-C2) group, an alkyleneoxy (C1-C2) group or an oxyalkylene (C1-C2) group, k is 0 or 1, R² is a hydrogen atom, a halogen atom, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-3 provided that when j is 2 or 3, R² is the same or different combination.
 4. An insecticidal composition comprising an insecticidally effective amount of a triazole derivative as defined in claim 1 and a carrier.
 5. An acaricidal composition comprising an acaricidally effective amount of a triazole derivative as defined in claim 2 and a carrier. 